Molding method, molding device, and article manufacturing method

Abstract

To provide a technique advantageous for reducing a failure generated in a composition in a processing of molding the composition on a substrate by using a molding.SOLUTION: In a molding method for hardening a composition in a state where the compositions on a molding and a substrate are made to be contacted, and molding the composition on the substrate by separating the molding from the composition to be hardened against each of a plurality of regions in the substrate, the plurality of regions contains: a first region that does not contain an outer edge part of the substrate; and a second region that contains the outer edge part. The composition on the substrate has a quality of an inhibition in hardening due to oxygen. In the processing, a gas supply operation for supplying a gas of which an oxygen concentration is lower than an air to between the molding and the substrate is suppressed before a contact of the molding and the substrate. A supply amount of the gas is smaller than the gas supply operation in the processing in the first region in the gas supply operation in the processing in the second region.SELECTED DRAWING: Figure 6

Description

[Technical field]

[0001] The present invention relates to a molding method, a molding apparatus, and a method for manufacturing an article. [Background technology]

[0002] As the demand for miniaturization of semiconductor devices increases, imprinting technology has been attracting attention in addition to conventional photolithography technology. Imprinting technology is a microfabrication technology that forms a pattern of imprinting material on a substrate by performing an imprinting process that uses a mold to mold an imprinting material (composition) on a substrate. For example, a photocuring method is one of the methods for hardening the imprinting material in the imprinting process. In the imprinting process using the photocuring method, the imprinting material on the substrate is hardened by irradiating the imprinting material with light while the mold and the imprinting material on the substrate are in contact with each other, and the mold is separated from the hardened imprinting material, thereby forming a pattern of the imprinting material on the substrate. By using such imprinting technology, a fine structure on the order of several nanometers can be formed on the substrate.

[0003] In the imprinting technique, when the mold and the imprinting material on the substrate are brought into contact with each other, air between the mold and the imprinting material may remain as air bubbles, causing defects in the pattern of the imprinting material formed on the substrate. Such defects are sometimes called pattern defects or unfilled defects. Patent Document 1 discloses a method for reducing pattern defects by supplying a gas that is highly soluble or highly diffusible in the imprinting material, or both, between the mold and the substrate. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Special Publication No. 2007-509769 Summary of the Invention [Problem to be solved by the invention]

[0005] The imprint process is performed on each of a plurality of shot areas on a substrate. In recent years, in order to improve the yield of product chips obtained from a substrate, it has become necessary to perform the imprint process on shot areas (so-called partial shot areas) including the outer edge portion of the substrate. The outer edge portion of the substrate may have warping or steps, and the imprint material may be supplied as droplets to such outer edge portions to prevent the mold from directly contacting the substrate. However, the droplets of the imprint material supplied to the outer edge portion of the substrate where warping or steps have occurred may not spread on the substrate due to insufficient contact (imprinting) of the mold, and a part of the droplets may remain attached to the mold after the imprint process. If the imprint material attached to the mold is in a hardened state, it may become a factor that causes pattern defects in the imprint process on the subsequent shot area.

[0006] Therefore, an object of the present invention is to provide an advantageous technique for reducing defects that occur in a composition during a process of molding the composition on a substrate using a mold. [Means for solving the problem]

[0007] In order to achieve the above-mentioned object, a molding method as one aspect of the present invention is a molding method in which a process of molding a composition on a substrate by hardening the composition while bringing a mold into contact with the composition, and separating the mold from the hardened composition, is performed on each of a plurality of regions on the substrate, the plurality of regions including a first region not including an outer edge portion of the substrate, and a second region including the outer edge portion, the composition on the substrate having a property such that hardening is inhibited by oxygen, and the process is characterized in that a gas supply operation is controlled to supply a gas having a lower oxygen concentration than air between the mold and the substrate before contacting the mold with the composition on the substrate, and the gas supply operation in the process of the second region supplies a smaller amount of gas than the gas supply operation in the process of the first region.

[0008] Further objects and other aspects of the present invention will become apparent from the following description of preferred embodiments with reference to the accompanying drawings. Effect of the Invention

[0009] According to the present invention, for example, an advantageous technique can be provided for reducing defects that occur in a composition during a process of molding the composition on a substrate using a mold. [Brief description of the drawings]

[0010] [Figure 1] 1 is a schematic diagram illustrating an example of the configuration of an imprint apparatus; [Diagram 2] FIG. 1 is a diagram showing an example of an arrangement of a plurality of shot areas on a substrate; [Diagram 3] 1 is a flowchart showing an imprint process according to a first embodiment; [Figure 4] FIG. 1 is a diagram for explaining a conventional imprint process; [Diagram 5] FIG. 1 is a diagram for explaining a conventional imprint process; [Figure 6] FIG. 1 is a diagram for explaining an imprint process according to a first embodiment; [Figure 7] FIG. 1 is a diagram for explaining an imprint process according to a first embodiment; [Figure 8] FIG. 1 is a diagram for explaining an example in which the remaining imprint material in an uncured state is cured due to a decrease in the oxygen concentration in the surroundings; [Figure 9] FIG. 1 is a diagram showing an example of an arrangement of a plurality of shot areas on a substrate; [Figure 10] FIG. 11 is a diagram for explaining an imprint process according to a second embodiment; [Figure 11] A diagram for explaining a method for manufacturing an article DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, the embodiments will be described in detail with reference to the attached drawings. Note that the following embodiments do not limit the invention according to the claims. Although the embodiments describe a number of features, not all of these features are essential to the invention, and the features may be combined in any manner. Furthermore, in the attached drawings, the same reference numbers are used for the same or similar configurations, and duplicated descriptions are omitted.

[0012] In this specification and the attached drawings, unless otherwise specified, directions are shown in an XYZ coordinate system in which the direction parallel to the surface of the substrate is the XY plane. The directions parallel to the X-axis, Y-axis, and Z-axis in the XYZ coordinate system are the X direction, Y direction, and Z direction, respectively, and the rotation around the X-axis, the Y axis, and the Z axis are θX, θY, and θZ, respectively. Control or drive regarding the X-axis, Y-axis, and Z-axis means control or drive regarding the direction parallel to the X-axis, the direction parallel to the Y axis, and the direction parallel to the Z axis, respectively. In addition, control or drive regarding the θX-axis, θY-axis, and θZ-axis means control or drive regarding the rotation around the axis parallel to the X-axis, the rotation around the axis parallel to the Y axis, and the rotation around the axis parallel to the Z axis, respectively. In addition, the position is information that can be specified based on the coordinates of the X-axis, Y-axis, and Z-axis, and the attitude is information that can be specified by the values ​​of the θX-axis, θY-axis, and θZ-axis.

[0013] The molding apparatus according to the present invention is an apparatus for performing a molding process in which a mold is pressed against a composition on a substrate to mold the composition. Examples of the molding apparatus include an imprinting apparatus and a planarizing apparatus. The imprinting apparatus is an apparatus for forming (transferring) a pattern in a composition (imprinting material) on a substrate by contacting a mold having a concave-convex pattern with the composition. The molding process performed by the imprinting apparatus is sometimes called an imprinting process. The planarizing apparatus is an apparatus for planarizing the surface of the composition on a substrate by contacting a mold having a flat surface with the composition. The molding process performed by the planarizing apparatus is sometimes called a planarizing process. In the following, an imprinting apparatus is exemplified as a molding apparatus, but the configuration and process of the imprinting apparatus can also be applied to the planarizing apparatus.

[0014] First Embodiment A first embodiment of the present invention will be described. An imprinting apparatus is a lithography apparatus that uses a mold to mold an imprinting material (composition) on a substrate, and can be employed in a lithography process that is a manufacturing process for devices such as semiconductor devices and magnetic storage media. The imprinting apparatus performs a process of forming a pattern of a cured material, to which a pattern of the mold is transferred, on the substrate by bringing an uncured imprinting material supplied on the substrate into contact with a mold and applying energy for curing to the imprinting material. This process is called an imprinting process, and is performed for each of a plurality of shot regions (imprinting regions) on the substrate. In this embodiment, an example is described that employs a photocuring method in which the imprinting material on the substrate is cured by irradiating the imprinting material with light (ultraviolet rays).

[0015] 1 is a schematic diagram showing an example of the configuration of an imprint apparatus 100 of this embodiment. The imprint apparatus 100 of this embodiment includes a light irradiation unit 1, a substrate stage 3, a mold holding unit 6, a liquid supply unit 9, a gas supply unit 10, and a control unit 11. The control unit 11 is configured by a computer (information processing device) having a processor such as a CPU (Central Processing Unit) and a storage unit such as a memory. The control unit 11 is connected to each part of the imprint apparatus 100 by a line, and controls each part of the imprint apparatus 100 (controls the imprint process).

[0016] During the imprint process, the light irradiation unit 1 (curing unit) irradiates the imprint material 7 with light 1a (e.g., ultraviolet light) while the mold 4 and the imprint material 7 on the substrate 2 (on the shot area) are in contact with each other, thereby curing the imprint material 7. The light irradiation unit 1 can include, for example, a light source and an optical element for adjusting the light emitted from the light source to light appropriate for the imprint process.

[0017] The mold holding unit 6 is a mechanism for moving the mold 4 in the Z direction while holding the mold 4. Specifically, the mold holding unit 6 may have a mold chuck for holding the mold 4, and a mold driving mechanism for driving the mold 4 (mold chuck). For example, the mold holding unit 6 can hold the mold 4 by attracting the outer edge region of the surface of the mold 4 irradiated with the light 1a by vacuum suction force or electrostatic force.

[0018] The mold holding unit 6 can drive the mold 4 in each axial direction so as to perform a pressing operation (imprinting operation) between the mold 4 and the imprint material 7 on the substrate 2, and a separating operation (mold releasing operation) of the mold 4 from the hardened imprint material 7 on the substrate 2. The mold holding unit 6 may be composed of a plurality of drive systems, such as a coarse movement drive system and a fine movement drive system, in order to accommodate high-precision positioning of the mold 4. The mold holding unit 6 may also be configured to have a position adjustment function for adjusting the position of the substrate 2 not only in the Z direction, but also in the X direction, Y direction, and rotation directions around each axis (θX, θY, θZ directions), and a tilt function for correcting the inclination of the mold 4. The imprinting operation and mold releasing operation in the imprint process may be realized by driving the mold 4 in the Z direction by the mold holding unit 6, or may be realized by driving the substrate 2 in the Z direction by the substrate stage 3 described later. Alternatively, the imprinting operation and the mold releasing operation may be realized by driving the mold 4 and the substrate 2 relatively in the Z direction by both the mold holding part 6 and the substrate stage 3.

[0019] The mold 4 held by the mold holding unit 6 usually has a rectangular outer peripheral shape and is made of a material capable of transmitting light 1a (ultraviolet rays), such as quartz glass. A mesa portion 5 configured in a mesa shape having a step of, for example, about several tens of nm is provided in a part of the surface of the mold 4 facing the substrate 2. The surface of the mesa portion 5 on the substrate 2 side functions as a molding surface (contact surface) that contacts the imprint material 7 on the substrate 2 and molds the imprint material 7. The molding surface of the mold 4 used in the imprinting device 100 is configured as a pattern surface on which a concave-convex pattern to be transferred to the imprint material 7 on the substrate 2, such as a circuit pattern, is formed three-dimensionally. Hereinafter, the mesa portion 5 on which the concave-convex pattern is formed may be referred to as a "pattern portion 5". The molding surface of the mold 4 used in the planarization device is configured as a flat surface on which no concave-convex pattern is formed.

[0020] The substrate stage 3 is a mechanism for moving the substrate 2 in the XY directions while holding the substrate 2. Specifically, the substrate stage 3 has a substrate chuck for holding the substrate 2, and a substrate driving mechanism for driving the substrate 2 (substrate chuck) in each axial direction. The substrate stage 3 can be used for aligning the mold 4 (pattern section 5) and the substrate 2 (shot area 8) when pressing the mold 4 against the imprint material 7 on the substrate 2 (shot area 8). The substrate stage 3 may be composed of a plurality of driving systems, such as a coarse motion driving system and a fine motion driving system, for each of the X and Y directions. The substrate stage 3 may also be configured to have a position adjustment function for adjusting the position of the substrate 2 not only in the XY directions, but also in the Z direction and the rotation directions around each axis (θX, θY, θZ directions), or a tilt function for correcting the inclination of the substrate 2.

[0021] Examples of materials used for the substrate 2 include glass, ceramics, metals, semiconductors, and resins. If necessary, a member made of a material different from that of the substrate 2 may be provided on the surface of the substrate 2. The substrate 2 may be, for example, a silicon wafer, a compound semiconductor wafer, or quartz glass. In the case of this embodiment, the substrate 2 is, for example, a single crystal silicon substrate or an SOI (Silicon on Insulator) substrate, and an imprint material 7 that is patterned by a mold 4 (pattern unit 5) is supplied (applied) onto the processing surface of the substrate 2.

[0022] The liquid supply unit 9 supplies the imprint material 7 as a plurality of droplets onto the substrate 2. The liquid supply unit 9 may be understood as a liquid ejection head that ejects (squirts) the imprint material 7 as a plurality of droplets toward the substrate 2. For example, while the substrate 2 is moved in the XY directions relative to the liquid supply unit 9 by the substrate stage 3 below the liquid supply unit 9, the liquid supply unit 9 is caused to eject the imprint material 7 as a plurality of droplets. This makes it possible to supply the imprint material 7 as a plurality of droplets onto the substrate 2 (shot region 8).

[0023] As the imprint material 7 supplied onto the substrate 2, a curable composition (sometimes called an uncured resin) that is cured by applying energy for curing is used. The curable composition is a composition that is cured by irradiation with light or by heating. Of these, the photocurable composition that is cured by irradiation with light contains at least a polymerizable compound and a photopolymerization initiator, and may further contain a non-polymerizable compound or a solvent as necessary. The non-polymerizable compound is at least one selected from the group consisting of a sensitizer, a hydrogen donor, an internal mold release agent, a surfactant, an antioxidant, and a polymer component. The viscosity of the viscous body (viscosity at 25° C.) is, for example, 1 mPa·s or more and 100 mPa·s or less. The imprint material 7 used in this embodiment has a property (characteristic) that its curing is inhibited by oxygen.

[0024] The gas supply unit 10 supplies the gas 10a to the space between the mold 4 and the substrate 2 so as to replace the space with the gas 10a. In the imprinting apparatus 100, when the mold 4 and the imprinting material 7 on the substrate 2 are brought into contact with each other in the air atmosphere, the air between the mold 4 and the imprinting material 7 may be mixed (residual) in the imprinting material 7 as air bubbles. In this case, the imprinting material 7 is not filled in the portion where the air bubbles are generated, and when the imprinting material 7 is cured in this state, a defect may occur in the pattern of the imprinting material 7 formed on the substrate 2. Such a defect may be called a pattern defect or an unfilled defect. Therefore, in the imprinting apparatus 100 of this embodiment, before the mold 4 and the imprinting material 7 on the substrate 2 are brought into contact with each other in the imprinting process, the gas supply unit 10 supplies the gas 10a between the mold 4 and the substrate 2. The gas 10a is a gas with a lower oxygen concentration than air, and may be, for example, a permeable gas that easily permeates the mold 4 or the imprinting material 7 during the imprinting operation. As the permeable gas, a rare gas such as helium (He) can be used. Here, the gas supply unit 10 is disposed around the mold 4 so as to surround the mold 4 held by the mold holding unit 6. The amount of gas 10a supplied between the mold 4 and the substrate 2 by the gas supply unit 10 is controlled by the control unit 11.

[0025] The imprint apparatus 100 configured as described above sequentially performs imprint processing on each of a plurality of shot regions 8 on the substrate 2, as shown in Fig. 2. In the imprint processing, after the mold 4 and the substrate 2 are positioned in a predetermined positional relationship, the mold holding unit 6 moves the mold 4 in the -Z direction to press (contact) the pattern portion 5 of the mold 4 against the imprint material 7 on the substrate 2 (shot region 8). Then, after the imprint material 7 is cured while the pattern portion 5 of the mold 4 and the imprint material 7 on the substrate 2 are in contact with each other, the mold 4 is separated from the cured imprint material 7 on the substrate 2. This allows a pattern made of the cured product of the imprint material 7 to be formed on the substrate 2.

[0026] Next, the imprint process of this embodiment will be described. Fig. 3 is a flowchart showing the imprint process of this embodiment. The flowchart in Fig. 3 can be executed by the control unit 11.

[0027] In step S101, the control unit 11 supplies the imprint material 7 as multiple droplets onto a target shot region 8 to be subjected to imprint processing (hereinafter, may be referred to as a target shot region 8) among the multiple shot regions 8 on the substrate 2. For example, the control unit 11 causes the liquid supply unit 9 to eject the imprint material 7 as multiple droplets while moving the substrate 2 in the XY directions by the substrate stage 3 below the liquid supply unit 9. This allows the imprint material 7 to be supplied as multiple droplets onto the target shot region 8 of the substrate 2.

[0028] In step S102, the control unit 11 moves the substrate 2 by the substrate stage 3 so that the target shot area 8 of the substrate 2 is disposed below the pattern portion 5 of the mold 4. Next, in step S103, the control unit 11 aligns the pattern portion 5 of the mold 4 with the target shot area 8 of the substrate 2 by adjusting the position of the substrate 2 in the XY directions by the substrate stage 3. This alignment can be performed based on the result of measuring the relative position between the alignment mark of the pattern portion 5 and the alignment mark of the target shot area 8 by an alignment measurement unit (not shown).

[0029] In step S104, the control unit 11 controls the gas supply operation of supplying the gas 10a between the mold 4 and the substrate 2 by the gas supply unit 10. As described above, the gas 10a is a gas with a lower oxygen concentration than air, and for example, helium can be used. Here, in this embodiment, the gas supply operation of step S104 is performed after step S102, but is not limited thereto. In the imprint apparatus 100, since the gap between the mold 4 and the substrate 2 is very small, it may be difficult for the gas supply unit 10 to supply the gas 10a between the mold 4 and the substrate 2 when the substrate 2 is disposed below the mold 4. Therefore, the gas supply operation of step S104 may be performed before step S102 in which the substrate 2 is moved below the mold 4, or in parallel with step S102. For example, the gas supply operation may be performed by supplying gas 10a below the mold 4 by the gas supply unit 10 before the substrate 2 is placed below the mold 4, and then moving the substrate 2 below the mold 4 when the area below the mold 4 is filled with gas 10a.

[0030] In step S105, the control unit 11 moves the mold 4 in the -Z direction using the mold holding unit 6, thereby bringing the mold 4 into contact with the imprint material 7 on the substrate 2. In step S106, while the mold 4 and the imprint material 7 on the substrate 2 are in contact with each other, the control unit 11 causes the light irradiation unit 1 to irradiate the imprint material with light 1a to harden it. Next, in step S107, the control unit 11 separates the mold 4 from the hardened imprint material 7 on the substrate 2 by moving the mold 4 in the +Z direction using the mold holding unit 6.

[0031] In step S108, the control unit 11 determines whether or not there is a shot area 8 on which imprint processing has not yet been performed, i.e., a shot area to be subjected to imprint processing next (hereinafter, may be referred to as the next shot area) on the substrate 2. If there is a next shot area, the process proceeds to step S101, and the control unit 11 performs imprint processing on the next shot area as the target shot area. On the other hand, if there is no next shot area, the process ends.

[0032] Incidentally, each of the multiple shot regions 8 in the substrate 2 can be roughly classified into an entire shot region 81 and a partial shot region 82, as shown in FIG. 2. The entire shot region 81 is a shot region 8 (first region) that is arranged in the central area of ​​the substrate 2 and does not include the outer edge portion 2a of the substrate 2. The entire pattern provided in the pattern portion 5 of the mold 4 is transferred to the entire shot region 81. On the other hand, the partial shot region 82 is a shot region 8 (second region) that is arranged in the peripheral area of ​​the substrate 2 and includes the outer edge portion 2a of the substrate 2. Only a part of the pattern provided in the pattern portion 5 of the mold 4 is transferred to the partial shot region 82. The entire shot region 81 may be called an entire shot region or a central shot region, and the partial shot region 82 may be called a missing shot region or a peripheral shot region.

[0033] In recent years, in order to improve the yield of product chips obtained from the substrate 2, it is required to perform imprint processing on the partial shot area 82 including the outer edge portion 2a of the substrate 2. In the imprint processing on the partial shot area 82, droplets of the imprint material 7 may be supplied onto the outer edge portion 2a of the substrate 2 as well in order to prevent the mold 4 from coming into direct contact with the substrate 2. However, the outer edge portion 2a of the substrate 2 may be warped (deflected) due to the shape of the substrate stage 3 (substrate chuck) or the suction pressure, or may have a step due to a pre-processing (for example, a patterning process for forming a base pattern). In addition, the outer edge portion of the substrate 2 may be subjected to chamfering (bevel processing). The droplets of the imprint material 7 supplied to such an outer edge portion may not spread on the substrate 2 due to insufficient contact (imprinting) of the mold 4, and some of the droplets may remain attached to the mold 4 after the imprint processing. Furthermore, if the imprint material 7 attached to the mold 4 is in a hardened state, it may become a factor that causes pattern defects in the imprint process for the subsequent shot area.

[0034] Therefore, the control unit 11 of this embodiment utilizes the property of the imprint material 7 that hardening is inhibited by oxygen to control the gas supply operation so as to avoid hardening of the imprint material 7 attached to the mold 4 by the imprint process of the partial shot region 82. Specifically, the control unit 11 controls the gas supply operation in the imprint process of the partial shot region 82 so that the amount of gas 10a supplied is less than that in the gas supply operation in the imprint process of the whole shot region 81. In other words, the gas supply operation is controlled so that the oxygen concentration around the partial shot region 82 when the imprint material 7 on the partial shot region 82 is hardened is higher than the oxygen concentration around the whole shot region 81 when the imprint material 7 in the whole shot region 81 is hardened.

[0035] This makes it possible to prevent some of the droplets of the imprint material 7 supplied to the outer edge portion 2a of the substrate 2 from adhering (remaining) in a hardened state to the pattern portion 5 of the mold 4 in the imprint process of the partial shot region 82. In other words, even if the imprint material 7 adheres to the pattern portion 5 of the mold 4 by the imprint process of the partial shot region 82, the imprint material 7 can be left in an unhardened state on the pattern portion 5 of the mold 4. The imprint material 7 remaining in an unhardened state on the pattern portion 5 of the mold 4 in this manner is integrated (mixed, merged, integrated) with the imprint material 7 on the shot region 8 (third region) where the next imprint process is performed. Therefore, the imprint material 7 remaining on the pattern portion 5 of the mold 4 is removed, and the occurrence of pattern defects in the imprint process for the subsequent shot region 8 can be reduced.

[0036] The imprinting process of this embodiment will be described below in comparison with a conventional imprinting process. Note that, in the following, the imprinting material 7 remaining attached to the pattern portion 5 of the mold 4 may be referred to as a “residual imprinting material 7′”.

[0037] First, a conventional imprint process will be described with reference to Fig. 4 to Fig. 5. Fig. 4 to Fig. 5 are diagrams for explaining the conventional imprint process. Fig. 4 shows an example in which warping occurs in the outer edge portion 2a of the substrate 2, and Fig. 5 shows an example in which a step occurs in the outer edge portion 2a of the substrate 2. Figs. 4 to 5 also show the steps corresponding to those in the flow chart of Fig. 3.

[0038] 4(a) to (d) and 5(a) to (d) show an example of a conventional imprint process of a partial shot area 82. As described above, the partial shot area 82 includes the outer edge portion 2a of the substrate 2 where warpage or a step occurs.

[0039] 4(a) and 5(a) show a state in which the pattern portion 5 of the mold 4 and the partial shot area 82 of the substrate 2 have been aligned through steps S101 to S103. The imprint material 7 is supplied as a plurality of droplets onto the partial shot area 82. As described above, droplets of the imprint material 7 are also supplied onto the outer edge portion 2a of the substrate 2 to prevent the mold 4 and the substrate 2 from coming into direct contact with each other.

[0040] 4(b) and 5(b) show a state in which the gas supply operation for the partial shot region 82 has been controlled through step S104. Conventionally, the same gas supply operation as that for the imprint process for the whole shot region 81 is performed in the imprint process for the partial shot region 82 as well. For example, conventionally, the gas supply operation in the imprint process for the partial shot region 82 is controlled so that the supply amount of the gas 10a is the same as that of the gas supply operation in the imprint process for the whole shot region 81. In other words, the gas supply operation is controlled so that the oxygen concentration around the partial shot region 82 when the imprint material 7 on the partial shot region 82 is hardened is the same as the oxygen concentration around the whole shot region 81 when the imprint material 7 in the whole shot region 81 is hardened.

[0041] 4(c) and 5(c) show a state in which the mold 4 and the imprint material 7 on the partial shot region 82 have come into contact with each other after step S105. At this time, the droplets of imprint material 7 supplied to the portion 2b of the partial shot region 82 other than the outer edge portion 2a are spread by the mold 4 (pattern portion 5) and filled between the mold 4 and the substrate 2. On the other hand, the droplets of imprint material 7 supplied to the outer edge portion 2a are not sufficiently spread by the mold 4, and the upper portions of the droplets are in slight contact with the mold 4. In this state, the imprint material 7 is irradiated with light 1a in step S105 and hardened.

[0042] 4(d) and 5(d) show a state in which the mold 4 has been separated from the hardened imprint material 7 on the partial shot region 82 after step S106. At this time, the droplets of the imprint material 7 on the outer edge portion 2a of the substrate 2 are not sufficiently spread out on the substrate 2, and therefore have insufficient adhesion to the substrate 2. As a result, some of the droplets of the imprint material 7 on the outer edge portion 2a adhere to the pattern portion 5 of the mold 4 and remain on the pattern portion 5 as residual imprint material 7'.

[0043] The remaining imprint material 7' in the conventional method is in a hardened state (cured state) due to irradiation with light 1a. Therefore, the next imprint process is performed with the remaining imprint material 7' in a hardened state attached to the pattern portion 5 of the mold 4. FIGS. 4(e) to (g) and 5(e) to (g) show an example of the next imprint process in the conventional method. In the following, a case where the next imprint process is an imprint process of a whole shot region 81 is illustrated, but the same applies to a case where the next imprint process is an imprint process of another partial shot region 82.

[0044] 4(e) and 5(e) show a state in which the gas supply operation for the entire shot region 81 has been controlled through steps S101 to S104. As described above, the gas supply operation for the entire shot region 81 is performed to prevent the occurrence of pattern defects (unfilled defects) caused by air being mixed into the imprint material 7 as air bubbles. As described above, the gas 10a supplied between the mold 4 and the substrate 2 in the gas supply operation is a gas with a lower oxygen concentration than air, and can be, for example, a permeable gas such as helium that easily permeates the mold 4 or the imprint material 7 during the imprinting operation.

[0045] 4(f) and 5(f) show a state where the mold 4 and the imprint material 7 on the whole shot region 81 come into contact with each other after step S105. Also, FIG. 4(g) and FIG. 5(g) show a state where the mold 4 is separated from the hardened imprint material 7 on the whole shot region 81 after step S106. Conventionally, the hardened remaining imprint material 7' attached to the mold 4 (pattern portion 5) comes into contact with the imprint material 7 spread over the whole shot region 81 by the mold 4. The hardened remaining imprint material 7' remains on the pattern portion 5 even after the mold 4 is separated from the hardened imprint material 7 on the whole shot region 81. As a result, a pattern defect (unfilled defect) may occur at a portion 7a of the hardened imprint material 7 on the whole shot region 81 where the hardened remaining imprint material 7' came into contact.

[0046] Next, the imprint process of this embodiment will be described with reference to Fig. 6 to Fig. 7. Fig. 6 to Fig. 7 are views for explaining the imprint process of this embodiment. Fig. 6 shows an example in which warping occurs in the outer edge portion 2a of the substrate 2, and Fig. 7 shows an example in which a step occurs in the outer edge portion 2a of the substrate 2. Also, Figs. 6 to 7 show the corresponding steps in the flowchart of Fig. 3.

[0047] 6(a) to (d) and 7(a) to (d) show examples of imprint processing of a partial shot area 82 in this embodiment. As described above, the partial shot area 82 includes the outer edge portion 2a of the substrate 2 where warpage and steps occur.

[0048] 6(a) and 7(a) show a state in which the pattern portion 5 of the mold 4 and the partial shot area 82 of the substrate 2 have been aligned through steps S101 to S103. The imprint material 7 is supplied as a plurality of droplets onto the partial shot area 82. As described above, droplets of the imprint material 7 are also supplied onto the outer edge portion 2a of the substrate 2 to prevent the mold 4 and the substrate 2 from coming into direct contact with each other.

[0049] 6(b) and 7(b) show a state in which the gas supply operation for the partial shot region 82 is controlled after step S104. In this embodiment, the gas supply operation in the imprint process for the partial shot region 82 is controlled so that the amount of gas 10a supplied between the mold 4 and the substrate 2 is smaller than that in the gas supply operation in the imprint process for the whole shot region 81. In other words, the gas supply operation is controlled so that the oxygen concentration around the partial shot region 82 when the imprint material 7 on the partial shot region 82 is cured is higher than the oxygen concentration around the whole shot region 81 when the imprint material 7 in the whole shot region 81 is cured. Specifically, in the imprint process for the partial shot region 82, the supply amount of gas 10a is controlled so that the remaining imprint material 7' attached to the mold 4 after the imprint process is inhibited from curing by the oxygen around it and remains in an uncured state. In the gas supply operation in the imprint process of the partial shot region 82, the gas 10a does not necessarily have to be supplied between the mold 4 and the substrate 2.

[0050] 6(c) and 7(c) show a state in which the mold 4 and the imprint material 7 on the partial shot region 82 are in contact with each other after the step S105. In the case of this embodiment, as described above, in the gas supply operation in the imprint process of the partial shot region 82, the amount of gas 10a supplied between the mold 4 and the substrate 2 is smaller than that in the gas supply operation in the imprint process of the whole shot region 81. Alternatively, the gas 10a is not supplied between the mold 4 and the substrate 2. Therefore, in the imprint process of the partial shot region 82, the time required for the imprint material 7 to be filled in the recesses of the pattern portion 5 of the mold 4 is longer than that in the imprint process of the whole shot region 81. Therefore, in the imprint process of the partial shot region 82, the waiting time (waiting time) for filling the recesses of the pattern portion 5 with the imprint material 7 may be longer than that in the imprint process of the whole shot region 81. The waiting time may be understood as the time from when the mold 4 and the imprint material 7 on the substrate 2 are brought into contact with each other until the imprint material starts to harden.

[0051] 6(d) and 7(d) show a state in which the mold 4 has been separated from the hardened imprint material 7 on the partial shot area 82 after step S106. At this time, some of the droplets of the imprint material 7 on the outer edge portion 2a adhere to the pattern portion 5 of the mold 4 and remain on the pattern portion 5 as residual imprint material 7'.

[0052] Here, as described above, the imprint material 7 contains at least a polymerizable compound and a photopolymerization initiator. The hardening of the imprint material 7 is caused by a polymerization reaction of the polymerizable compound caused by radicals generated from the photopolymerization initiator irradiated with light 1a (ultraviolet rays). Oxygen reacts with the radicals generated from the photopolymerization initiator by irradiation with light 1a (ultraviolet rays) and eliminates the radicals. This inhibits the polymerization reaction of the polymerizable compound. This means that the hardening of the imprint material 7 is inhibited by oxygen.

[0053] In the imprint process of the partial shot region 82 in this embodiment, the amount of gas 10b supplied in the gas supply operation is smaller than that in the imprint process of the whole shot region 81, and therefore the concentration of gas 10b between the mold 4 and the substrate 2 is lower. That is, in the imprint process of the partial shot region 82, the oxygen concentration between the mold 4 and the substrate 2 is higher than that in the imprint process of the whole shot region 81.

[0054] The droplets of the imprint material 7 supplied to the portion 2b of the partial shot region 82 other than the outer edge portion 2a are spread by the mold 4 (pattern portion 5) and filled between the pattern portion 5 and the partial shot region 82. At this time, oxygen is pushed out from between the pattern portion 5 and the imprint material 7 on the portion 2b, so that the imprint material 7 on the portion 2b can be cured by irradiation with the light 1b (ultraviolet light). On the other hand, the droplets of the imprint material 7 supplied to the outer edge portion 2a are inhibited (suppressed) from being cured by oxygen because an oxygen-containing atmosphere is present around them. When the gas 10a is not supplied between the mold 4 and the substrate 2 in the gas supply operation of step S104, the oxygen concentration around the droplets of the imprint material 7 supplied to the outer edge portion 2a becomes higher, and the effect of inhibiting (suppressing) the curing of the droplets of the imprint material 7 becomes higher.

[0055] Thus, in this embodiment, the remaining imprint material 7' adhering to the mold 4 (pattern portion 5) remains in an uncured state, and the next imprint process is performed with the remaining uncured imprint material 7' adhering to the mold 4. If the amount of the remaining uncured imprint material 7' adhering to the mold 4 is small, it volatilizes and disappears over time, so there is a low possibility of causing pattern defects in the next imprint process. Furthermore, even if the next imprint process is performed before the remaining uncured imprint material 7' adhering to the mold 4 disappears, it is integrated (mixed, merged, integrated) with the imprint material 7 supplied onto the substrate 2 in the next imprint process. Therefore, it is possible to perform the next imprint process without waiting until the remaining uncured imprint material 7' disappears.

[0056] 6(e) to (g) and 7(e) to (g) show an example of the next imprint process in this embodiment. In the following, a case where the next imprint process is an imprint process of a whole shot region 81 is illustrated, but the same applies to the case where the next imprint process is an imprint process of another partial shot region 82.

[0057] 6(e) and 7(e) show a state in which the gas supply operation for the whole shot region 81 is controlled through steps S101 to S104. As described above, in the gas supply operation for the whole shot region 81, gas 10a is supplied between the mold 4 and the substrate 2 so as to prevent the occurrence of pattern defects (unfilled defects) caused by air being mixed as air bubbles into the imprint material 7. In other words, the gas supply operation for the whole shot region 81 is controlled so that the amount of gas 10a supplied is greater than that in the gas supply operation for the partial shot region 82.

[0058] 6(f) and 7(f) show a state in which the mold 4 and the imprint material 7 on the whole shot region 81 come into contact with each other after step S105. Also, FIG. 4(g) and FIG. 5(g) show a state in which the mold 4 is separated from the hardened imprint material 7 on the whole shot region 81 after step S106. In the case of this embodiment, the remaining imprint material 7' adhering to the pattern portion 5 of the mold 4 is in an unhardened state. Therefore, when the mold 4 (pattern portion 5) and the imprint material 7 on the whole shot region 81 come into contact with each other, the remaining imprint material 7' is integrated with the imprint material 7 on the whole shot region 81. Therefore, it is possible to reduce the occurrence of pattern defects (unfilled defects) caused by the remaining imprint material 7' in the hardened imprint material 7 on the whole shot region 81.

[0059] As described above, in this embodiment, the gas supply operation in the imprint process of the partial shot region 82 is controlled so that the amount of gas 10a supplied is less than that in the gas supply operation in the imprint process of the whole shot region 81. This makes it possible to keep the remaining imprint material 7' attached to the pattern portion 5 of the mold 4 in the imprint process of the partial shot region 82 in an uncured state. As a result, it is possible to reduce the occurrence of pattern defects caused by the remaining imprint material 7' in the subsequent imprint process. In other words, it is possible to reduce defects occurring in the imprint material 7 on the substrate 2 in the imprint process.

[0060] <Second embodiment> A second embodiment of the present invention will be described. This embodiment basically follows the first embodiment, and can follow the first embodiment except for the points mentioned below.

[0061] The remaining uncured imprint material 7' attached to the mold 4 (pattern portion 5) may undergo a curing reaction when the oxygen concentration in its vicinity decreases. For example, the imprint material 7 has a property that, once irradiated with light 1a (ultraviolet rays) and the reaction of the photopolymerization initiator starts, the polymerization reaction proceeds and the material hardens when the oxygen concentration in its vicinity decreases. Therefore, even if the remaining imprint material 7' is in an uncured state immediately after the imprint process of the partial shot region 82 is completed, it may harden due to a decrease in the oxygen concentration in its vicinity.

[0062] 8 shows an example in which the remaining imprint material 7', which is in an uncured state immediately after the imprint process of the partial shot region 82 is completed, is cured due to a decrease in the oxygen concentration in the surrounding area. Fig. 8(a) shows a state in which the mold 4 is separated from the cured imprint material 7 on the partial shot region 82 through steps S101 to S106. At this time, some of the droplets of the imprint material 7 on the outer edge portion 2a adhere to the mold 4 (pattern portion 5) and remain on the mold 4 as the remaining imprint material 7' in an uncured state.

[0063] 8(b) to (d) show an example in which the next imprint process is performed on the whole shot region 81. Fig. 8(b) shows a state in which the gas supply operation for the whole shot region 81 is controlled through steps S101 to S104. Fig. 8(c) shows a state in which the mold 4 and the imprint material 7 on the whole shot region 81 are in contact with each other through step S105. Fig. 8(d) shows a state in which the mold 4 is separated from the hardened imprint material 7 on the whole shot region 81 through step S106.

[0064] As described above, in the gas supply operation for the entire shot region 81, the gas 10a is supplied between the mold 4 and the substrate 2 so as to prevent the occurrence of pattern defects (unfilled defects) caused by air being mixed into the imprint material 7 as air bubbles. That is, the gas supply operation for the entire shot region 81 is controlled so that the amount of gas 10a supplied is greater than that for the partial shot region 82. At this time, the oxygen concentration around the remaining imprint material 7' in an uncured state adhering to the pattern portion 5 of the mold 4 decreases, so that the curing reaction of the remaining imprint material 7' may progress to a cured state. The remaining imprint material 7' in a cured state remains on the pattern portion 5 even after the mold 4 is separated from the cured imprint material 7 on the entire shot region 81. As a result, a pattern defect (unfilled defect) may occur at the portion 7a of the cured imprint material 7 on the entire shot region 81 where the remaining imprint material 7' in a cured state was in contact.

[0065] Therefore, in this embodiment, following the imprint process of the partial shot region 82, an imprint process (hereinafter, sometimes referred to as a specific imprint process) is performed to remove the remaining imprint material 7' adhering to the pattern portion 5 of the mold 4. The supply amount of the gas 10a in the gas supply operation of the specific imprint process is controlled to be less than the supply amount of the normal gas 10a in the gas supply operation of the imprint process of the whole shot region 81. In the gas supply operation of the specific imprint process, the gas 10a does not need to be supplied between the mold 4 and the substrate 2.

[0066] 9, the specific imprint processing is performed on a whole shot area 83 (third area) that is disposed in the central area of ​​the substrate 2 and does not include the outer edge portion 2a of the substrate 2, among the multiple shot areas 8 on the substrate 2. Here, the whole shot area 83 on which the specific imprint processing is performed may be the shot area 8 on which the imprint processing is performed last, among the multiple shot areas 8 on the substrate 2. Alternatively, the imprint processing may be performed on another whole shot area 81 after the whole shot area 83 on which the specific imprint processing is performed.

[0067] Next, the imprint processing of this embodiment will be described with reference to Fig. 10. Here, an example will be described in which imprint processing is performed on another whole shot region 81 after a whole shot region 83 on which a specific imprint processing is performed.

[0068] 10(a) shows a state in which the mold 4 has been separated from the hardened imprint material 7 on the partial shot region 82 through steps S101 to S106. At this time, some of the droplets of the imprint material 7 on the outer edge portion 2a adhere to the mold 4 (pattern portion 5) and remain on the mold 4 as unhardened residual imprint material 7'.

[0069] 10(b) to (d) show an example in which a specific imprint process is performed on the whole shot region 83. FIG. 10(b) shows a state in which the gas supply operation for the whole shot region 83 is controlled through steps S101 to S104 in the specific imprint process. In the case of this embodiment, the supply amount of the gas 10a in the gas supply operation of the specific imprint process is controlled to be less than the supply amount of the gas 10a in the gas supply operation of the imprint process of another whole shot region 81. That is, the oxygen concentration around the whole shot region 83 when the imprint material 7 on the whole shot region 83 is cured in the specific imprint process is higher than the oxygen concentration around the whole shot region 81 when the imprint material 7 on the whole shot region 81 is cured. Specifically, in the specific imprint process, the supply amount of the gas 10a is controlled so that the remaining imprint material 7' attached to the mold 4 is inhibited from curing by the surrounding oxygen and remains in an uncured state. In the gas supplying operation of a particular imprint process, the gas 10a does not necessarily need to be supplied between the mold 4 and the substrate 2.

[0070] FIG. 10(c) shows a state in which the mold 4 and the imprint material 7 on the whole shot region 81 come into contact with each other after step S105 in the specific imprint process. FIG. 10(d) shows a state in which the mold 4 is separated from the hardened imprint material 7 on the whole shot region 81 after step S106 in the specific imprint process. The specific imprint process is performed in a state in which the oxygen concentration between the mold 4 and the substrate 2 is relatively high. Therefore, the hardening reaction of the remaining imprint material 7' adhering to the mold 4 is inhibited by oxygen, and the remaining imprint material 7' can be integrated with the imprint material 7 on the substrate 2 while remaining in an unhardened state. This makes it possible to remove the remaining imprint material 7' adhering to the mold 4.

[0071] 10(e)-(g) show an example in which imprint processing is performed on another whole shot region 81. FIG. 10(e) shows a state in which the gas supply operation on the whole shot region 81 is controlled through steps S101-S104. FIG. 10(f) shows a state in which the mold 4 and the imprint material 7 on the whole shot region 81 are in contact with each other through step S105. FIG. 10(g) shows a state in which the mold 4 is separated from the hardened imprint material 7 on the whole shot region 81 through step S106. In this embodiment, since the remaining imprint material 7' of the mold 4 is removed by the specific imprint processing described above, it is possible to reduce the occurrence of pattern defects caused by the remaining imprint material 7' in the imprint processing on another whole shot region 81.

[0072] <Third embodiment> A third embodiment of the present invention will be described. In this embodiment, the order of imprint processing (including specific imprint processing) for multiple shot areas 8 on a substrate 2 will be described with reference to FIG. 9. FIG. 9 shows the arrangement of multiple shot areas 8 on a substrate 2. As shown in FIG. 9, the multiple shot areas 8 on a substrate 2 may include multiple whole shot areas 81 shown in white, multiple partial shot areas 82 shown in gray, and a whole shot area 83 shown with hatching. The whole shot area 83 shown with hatching is a shot area 8 on which a specific imprint processing is performed as described in the second embodiment. Note that this embodiment basically follows the second embodiment, and may follow the second embodiment except for the matters mentioned below.

[0073] [Example 1] In the first embodiment, an example will be described in which the entire shot area 83 on which the specific imprint processing is performed is the shot area 8 on which the imprint processing is last performed among the multiple shot areas 8 on the substrate 2.

[0074] In this embodiment 1, first, imprint processing is performed on each of the multiple whole shot regions 81 shown in white in Fig. 9. In the gas supply operation in the imprint processing of each whole shot region 81, as described above, a sufficient amount of gas 10a is supplied between the mold 4 and the substrate 2 so as to prevent the occurrence of pattern defects caused by air being mixed into the imprint material 7 as bubbles. The supply amount of gas 10a is preferably set so that the filling time required for the imprint material 7 to be filled into the recesses of the mold 4 (pattern portion 5) is shorter than a desired time, and the number of pattern defects caused by bubbles is less than a desired number. Note that the order in which imprint processing is performed on the multiple whole shot regions 81 may be arbitrary.

[0075] After the imprint process for all the whole shot regions 81 is completed, the imprint process is then performed on the multiple partial shot regions 82 shown in gray in FIG. 9. As described above, the gas supply operation in the imprint process for each partial shot region 82 is controlled so that the amount of gas 10a supplied between the mold 4 and the substrate 2 is less than that in the gas supply operation in the imprint process for each whole shot region 81. The amount of gas 10a supplied is controlled so that the hardening of the remaining imprint material 7' attached to the mold 4 (pattern portion 5) is inhibited by oxygen. For example, in the gas supply operation in the imprint process for each partial shot region 82, the gas 10a may not be supplied between the mold 4 and the substrate 2. The remaining imprint material 7' attached to the mold 4 by the imprint process for the partial shot region 82 is in an unhardened state, and is therefore integrated with the imprint material 7 on the substrate 2 in the next imprint process. Therefore, in the next imprint process, the occurrence of pattern defects caused by the remaining imprint material 7' can be reduced. The order in which imprint processing is performed on the multiple partial shot regions 82 may be arbitrary.

[0076] When the imprint processing for all the partial shot regions 82 is completed, finally, the specific imprint processing is performed on the whole shot region 83 shown by hatching in FIG. 9. As described above, the gas supply operation in the specific shot region is controlled so that the amount of gas 10a supplied between the mold 4 and the substrate 2 is smaller than the gas supply operation in the imprint processing of each whole shot region 81. For example, the gas supply operation in the specific shot region may supply the same amount of gas 10a as the gas supply operation in the imprint processing of each partial shot region 82, or the gas 10a may not be supplied between the mold 4 and the substrate 2. By performing this specific imprint processing, the imprint processing of the substrate 2 is completed in a state where the remaining imprint material 7' attached to the mold 4 by the imprint processing of the partial shot region 82 is removed, and the imprint processing of the next substrate can be continued.

[0077] [Example 2] In the second embodiment, an example will be described in which a specific imprint process is performed on a whole shot region 83, and then an imprint process is performed on the remaining whole shot region 81.

[0078] In this Example 2, first, imprint processing is performed on the multiple partial shot areas 82 shown in gray in Fig. 9. The imprint processing of each partial shot area 82 is as explained in Example 1 above, and therefore the explanation here is omitted. Note that the order in which imprint processing is performed on the multiple partial shot areas 82 can be arbitrary.

[0079] When the imprint processing for all partial shot regions 82 is completed, next, a specific imprint processing is performed on the whole shot region 83 shown by hatching in Fig. 9. The specific imprint processing for the whole shot region 83 is as explained in the above Example 1 and so on, and therefore an explanation thereof will be omitted here. By performing this specific imprint processing, the remaining imprint material 7' adhered to the mold 4 by the imprint processing for the partial shot region 82 can be removed.

[0080] When the specific imprint process for the whole shot region 83 is completed, finally, the imprint process is performed for each of the whole shot regions 81 shown in white in Fig. 9. The imprint process for each whole shot region 81 is as explained in the above Example 1, and therefore the explanation here will be omitted.

[0081] After (immediately after) the imprint process of the whole shot region 81, the gas 10a remains between the mold 4 and the substrate 2, that is, the oxygen concentration between the mold 4 and the substrate 2 is relatively low. Therefore, if the imprint process of the partial shot region 82 is performed following the imprint process of the whole shot region 81, it is difficult to ensure a sufficient oxygen concentration between the mold 4 and the substrate 2 to inhibit the hardening of the remaining imprint material 7' adhering to the mold 4. In other words, there is a risk that the remaining imprint material 7' adhering to the mold 4 will harden. In this embodiment 2, the imprint process of each partial shot region 82 is performed before the imprint process of each whole shot region 81, so that the hardening of the remaining imprint material 7' adhering to the mold 4 can be suppressed and the occurrence of pattern defects can be reduced.

[0082] <Embodiment of the article manufacturing method> The method for manufacturing an article according to an embodiment of the present invention is suitable for manufacturing an article such as a microdevice such as a semiconductor device or an element having a fine structure. The method for manufacturing an article according to the present embodiment includes a molding step of molding a composition on a substrate using the above molding method with a molding device, a processing step of processing the substrate having the composition molded in the molding step, and a manufacturing step of manufacturing an article from the substrate processed in the processing step. An imprinting device or a planarizing device may be used as the molding device. Furthermore, such a manufacturing method includes other well-known steps (oxidation, film formation, deposition, doping, planarization, etching, resist stripping, dicing, bonding, packaging, etc.). The method for manufacturing an article according to the present embodiment is advantageous in at least one of the performance, quality, productivity, and production cost of the article compared to conventional methods.

[0083] The pattern of the cured product molded using the above molding device is used permanently as at least a part of various articles, or temporarily when manufacturing various articles. The articles are electric circuit elements, optical elements, MEMS, recording elements, sensors, or molds. Examples of electric circuit elements include volatile or non-volatile semiconductor memories such as DRAM, SRAM, flash memory, and MRAM, and semiconductor elements such as LSI, CCD, image sensors, and FPGA. Examples of molds include molds for imprinting.

[0084] The pattern of the cured product is used as it is as at least a part of a component of the article, or is used temporarily as a resist mask, which is removed after etching or ion implantation in a substrate processing step.

[0085] Next, a specific method for manufacturing an article using an imprinting apparatus as a molding apparatus will be described. As shown in Fig. 11(a), a substrate 1z such as a silicon wafer having a workpiece 2z such as an insulator formed on its surface is prepared, and then an imprinting material 3z is applied to the surface of the workpiece 2z by an inkjet method or the like. Here, a state in which multiple droplets of the imprinting material 3z are applied onto the substrate is shown.

[0086] As shown in Fig. 11(b), the imprinting mold 4z is placed so that the side on which the concave-convex pattern is formed faces the imprinting material 3z on the substrate. As shown in Fig. 11(c), the substrate 1z to which the imprinting material 3z has been applied is brought into contact with the mold 4z, and pressure is applied. The imprinting material 3z fills the gap between the mold 4z and the workpiece 2z. When light is irradiated through the mold 4z in this state as energy for curing, the imprinting material 3z is cured.

[0087] 11(d), after the imprint material 3z is cured, the mold 4z and the substrate 1z are separated, and a pattern of the cured product of the imprint material 3z is formed on the substrate 1z. In this cured product pattern, the recesses of the mold correspond to the protrusions of the cured product, and the protrusions of the mold correspond to the recesses of the cured product, i.e., the recessed and protruding pattern of the mold 4z is transferred to the imprint material 3z.

[0088] As shown in Fig. 11(e), when etching is performed using the pattern of the cured material as an etching-resistant mask, the portion of the surface of the workpiece 2z where there is no cured material or where only a thin layer remains is removed, forming a groove 5z. As shown in Fig. 11(f), when the pattern of the cured material is removed, an article having grooves 5z formed on the surface of the workpiece 2z can be obtained. Here, the pattern of the cured material is removed, but it may be used as an interlayer insulating film included in a semiconductor element or the like, that is, a component of an article, without being removed after processing.

[0089] <Summary of the embodiment> The disclosure of the present specification includes at least the following molding method, molding apparatus, and method of manufacturing an article. (Item 1) A molding method comprising the steps of: curing a composition on a substrate while contacting the composition with a mold; and separating the mold from the cured composition to mold the composition on the substrate, for each of a plurality of regions on the substrate, the method comprising the steps of: the plurality of regions include a first region that does not include an outer edge portion of the substrate and a second region that includes the outer edge portion; The composition on the substrate has a property that hardening is inhibited by oxygen, In the process, a gas supply operation is controlled to supply a gas having an oxygen concentration lower than that of air between the mold and the substrate before contacting the mold with the composition on the substrate; A molding method, characterized in that, in the gas supplying operation in the treatment of the second area, the amount of gas supplied is smaller than that in the gas supplying operation in the treatment of the first area. (Item 2) 2. The molding method according to item 1, characterized in that, in the gas supply operation in the treatment of the second region, the supply amount of the gas is controlled so that the oxygen concentration around the second region when the composition on the second region is hardened is higher than the oxygen concentration around the first region when the composition on the first region is hardened. (Item 3) 3. The molding method according to item 1 or 2, characterized in that, in the gas supplying operation in the treatment of the second region, the amount of the gas supplied is controlled so that the composition adhering to the mold after the treatment of the second region is inhibited from curing by oxygen surrounding the second region and remains in an uncured state. (Item 4) 4. The molding method according to any one of items 1 to 3, wherein the gas supply operation in the processing of the second region does not include supplying the gas between the mold and the substrate. (Item 5) 5. The molding method according to any one of items 1 to 4, characterized in that in the treatment of the second region, the time from contacting the mold with the composition on the substrate to starting hardening of the composition is longer than in the treatment of the first region. (Item 6) The plurality of regions further includes a third region that does not include the outer edge portion, the processing of the third region is performed subsequent to the processing of the second region; The molding method according to any one of items 1 to 5, characterized in that the gas supply operation in the treatment of the third area supplies a smaller amount of gas than the gas supply operation in the treatment of the first area. (Item 7) In the gas supply operation in the treatment of the second region, the supply amount of the gas is controlled so that the composition adhering to the mold after the treatment of the second region is inhibited from curing by oxygen around the second region and remains in an uncured state; 7. The molding method according to item 6, wherein in the gas supplying operation in the treatment of the third region, the amount of gas supplied is controlled so that the composition adhering to the mold after the treatment of the second region is inhibited from curing by oxygen surrounding the third region and remains uncured and integrated with the composition on the third region. (Item 8) 8. The molding method according to item 6 or 7, wherein the third region is the region among the plurality of regions where the treatment is performed last. (Item 9) 8. The molding method according to item 6 or 7, characterized in that the treatment of the first region is performed after the treatment of the third region. (Item 10) A molding method comprising the steps of: curing a composition on a substrate while contacting the composition with a mold; and separating the mold from the cured composition to mold the composition on the substrate, for each of a plurality of regions on the substrate, the method comprising the steps of: the plurality of regions include a first region that does not include an outer edge portion of the substrate and a second region that includes the outer edge portion; The composition on the substrate has a property that hardening is inhibited by oxygen, A molding method, characterized in that the oxygen concentration around the second region when the composition on the second region is hardened is higher than the oxygen concentration around the first region when the composition on the first region is hardened. (Item 11) A molding step of molding a composition on a substrate using the molding method according to any one of items 1 to 10; a processing step of processing the substrate having the composition molded in the molding step; a manufacturing process for manufacturing an article from the substrate processed in the processing process; A method for manufacturing an article, comprising: (Item 12) A molding apparatus for performing a process of molding a composition on a substrate by contacting a mold with the composition on the substrate and curing the composition while the mold is in contact with the composition, and then separating the mold from the cured composition, for each of a plurality of regions on the substrate, the process comprising: a supply unit that supplies a gas having an oxygen concentration lower than that of air between the mold and the substrate; A control unit for controlling the processing; Equipped with the plurality of regions include a first region that does not include an outer edge portion of the substrate and a second region that includes the outer edge of the substrate; The composition on the substrate has a property that hardening is inhibited by oxygen, In the process, before the mold and the composition on the substrate are brought into contact with each other, a gas supply operation for supplying the gas by the supply unit is controlled; A molding apparatus characterized in that the control unit controls the gas supply operation in the processing of the second area so that the amount of gas supplied is less than the gas supply operation in the processing of the first area. (Item 13) A molding apparatus for performing a process of molding a composition on a substrate by contacting a mold with the composition on the substrate and curing the composition while the mold is in contact with the composition, and then separating the mold from the cured composition, for each of a plurality of regions on the substrate, the process comprising: a supply unit that supplies a gas having an oxygen concentration lower than that of air between the mold and the substrate; A control unit for controlling the processing; Equipped with the plurality of regions include a first region that does not include an outer edge portion of the substrate and a second region that includes the outer edge portion; The composition on the substrate has a property that hardening is inhibited by oxygen, A molding apparatus characterized in that the control unit controls the supply unit so that the oxygen concentration around the second region when the composition on the second region is hardened is higher than the oxygen concentration around the first region when the composition on the first region is hardened.

[0090] The invention is not limited to the above-described embodiments, and various modifications and variations are possible without departing from the spirit and scope of the invention. Accordingly, the following claims are appended to apprise the public of the scope of the invention. [Explanation of symbols]

[0091] 2: substrate, 3: substrate stage, 4: mold, 5: pattern section, 6: mold holding section, 7: imprint material, 8: shot area, 9: liquid supply section, 10: gas supply section

Claims

1. A molding method comprising the steps of: curing a composition on a substrate while contacting the composition with a mold; and separating the mold from the cured composition to mold the composition on the substrate, for each of a plurality of regions on the substrate, the method comprising the steps of: the plurality of regions include a first region that does not include an outer edge portion of the substrate and a second region that includes the outer edge portion; The composition on the substrate has a property that hardening is inhibited by oxygen, In the process, a gas supply operation is controlled to supply a gas having an oxygen concentration lower than that of air between the mold and the substrate before contacting the mold with the composition on the substrate; A molding method, characterized in that, in the gas supplying operation in the treatment of the second area, the amount of gas supplied is smaller than that in the gas supplying operation in the treatment of the first area.

2. The molding method according to claim 1, characterized in that, in the gas supply operation in the treatment of the second region, the amount of gas supplied is controlled so that the oxygen concentration around the second region when the composition on the second region is hardened is higher than the oxygen concentration around the first region when the composition on the first region is hardened.

3. The molding method according to claim 1, characterized in that, during the gas supply operation in the treatment of the second area, the amount of gas supplied is controlled so that the composition adhering to the mold after the treatment of the second area is inhibited from hardening by oxygen surrounding the second area and remains in an unhardened state.

4. The molding method according to claim 1 , wherein the gas supplying operation in the processing of the second region does not supply the gas between the mold and the substrate.

5. The molding method according to claim 1, characterized in that in the treatment of the second region, the time from contacting the mold with the composition on the substrate to the start of hardening of the composition is longer than in the treatment of the first region.

6. The plurality of regions further includes a third region that does not include the outer edge portion, the processing of the third region is performed subsequent to the processing of the second region; The molding method according to claim 1 , wherein the gas supplying operation in the treatment of the third region supplies a smaller amount of gas than the gas supplying operation in the treatment of the first region.

7. In the gas supply operation in the treatment of the second region, the supply amount of the gas is controlled so that the composition adhering to the mold after the treatment of the second region is inhibited from curing by oxygen around the second region and remains in an uncured state; The molding method according to claim 6, characterized in that, in the gas supply operation in the treatment of the third area, the amount of gas supplied is controlled so that the composition adhering to the mold after the treatment of the second area is inhibited from curing by oxygen surrounding the third area and remains uncured and integrated with the composition on the third area.

8. The molding method according to claim 6 , wherein the third region is the last of the plurality of regions to be subjected to the treatment.

9. The molding method according to claim 6 , wherein the treatment of the first region is performed after the treatment of the third region.

10. A molding method comprising the steps of: curing a composition on a substrate while contacting the composition with a mold; and separating the mold from the cured composition to mold the composition on the substrate, for each of a plurality of regions on the substrate, the method comprising the steps of: the plurality of regions include a first region that does not include an outer edge portion of the substrate and a second region that includes the outer edge portion; The composition on the substrate has a property that hardening is inhibited by oxygen, A molding method, characterized in that the oxygen concentration around the second region when the composition on the second region is hardened is higher than the oxygen concentration around the first region when the composition on the first region is hardened.

11. A molding step of molding a composition on a substrate using the molding method according to any one of claims 1 to 10; a processing step of processing the substrate having the composition molded in the molding step; a manufacturing process for manufacturing an article from the substrate processed in the processing process; A method for manufacturing an article, comprising:

12. A molding apparatus for performing a process of molding a composition on a substrate by contacting a mold with the composition on the substrate and curing the composition while the mold is in contact with the composition, and then separating the mold from the cured composition, for each of a plurality of regions on the substrate, the process comprising: a supply unit that supplies a gas having an oxygen concentration lower than that of air between the mold and the substrate; A control unit for controlling the processing; Equipped with the plurality of regions include a first region not including an outer edge portion of the substrate and a second region including the outer edge of the substrate; The composition on the substrate has a property that hardening is inhibited by oxygen, In the process, before the mold and the composition on the substrate are brought into contact with each other, a gas supply operation for supplying the gas by the supply unit is controlled; A molding apparatus characterized in that the control unit controls the gas supply operation in the processing of the second area so that the amount of gas supplied is less than the gas supply operation in the processing of the first area.

13. A molding apparatus for performing a process of molding a composition on a substrate by contacting a mold with the composition on the substrate and curing the composition while the mold is in contact with the composition, and then separating the mold from the cured composition, for each of a plurality of regions on the substrate, the process comprising: a supply unit that supplies a gas having an oxygen concentration lower than that of air between the mold and the substrate; A control unit for controlling the processing; Equipped with the plurality of regions include a first region that does not include an outer edge portion of the substrate and a second region that includes the outer edge portion; The composition on the substrate has a property that hardening is inhibited by oxygen, The molding apparatus, characterized in that the control unit controls the supply unit so that the oxygen concentration around the second region when the composition on the second region is hardened is higher than the oxygen concentration around the first region when the composition on the first region is hardened.

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